JPH02279603A - Agricultural chemical solid formulation - Google Patents

Abstract

PURPOSE:To obtain an agricultural chemical solid formulation with extremely rare deterioration in physical properties even when preserved for a long period by thermally melting a technical product of an agricultural chemical having the melting point within a specific range and a water-soluble polymer capable of assuming a solid form at ambient temperature, cooling and solidifying the resultant molten mixture and then adding a mineral carrier thereto. CONSTITUTION:An agricultural chemical solid formulation obtained by, as necessary, adding a surfactant and/or a solvent to a technical product of an agricultural chemical having 0 to 70 deg.C melting point and a water-soluble polymer selected from polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxybutylene glycol and polyoxyethylene polyoxypropylene polyoxybutylene glycol assuming a solid form at ambient temperature, thermally melting both ingredient, cooling and solidifying the resultant molten mixture, then adding a mineral carrier thereto and further, as necessary, adding and mixing an adjuvant for the formulation therewith. Alternately, the mineral carrier is added to the molten mixture and the obtained mixture is subsequently cooled and solidified to afford a similar formulation.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a solid agrochemical preparation of an agrochemical raw material having a melting point of 0 to 70°C.

<Conventional technology and problems to be solved> Conventionally, agricultural chemical ingredients are semi-solid at room temperature, that is, with a melting point of 0 to 70.
There are two ways to make a pesticide active ingredient into a solid formulation: one method is to treat the active ingredient as a liquid, and the other is to treat it as a solid.

When handled as a liquid, it is necessary to heat the active ingredient to dissolve it completely, and when handled as a one-sided solid, it is difficult to melt the active ingredient and cause aggregation due to it during processes that generate heat, such as the crushing process. Caution must be taken. When the agricultural chemical solid formulation obtained in this way is stored for a long period of time, the physical properties may deteriorate due to the growth of crystals of the active ingredient particles as a result of the repeated state changes between liquid and solid state of the active ingredient. For example, in wettable powders, the suspension rate and fineness decrease, in powders, caking during storage, in granular wettable powders, disintegration and dispersion in water, in suspension rate and fineness decrease, and in granules, dosage release after dispersion. Sometimes it appears as a change in quantity.

In addition, in order to solve these problems, a method has been reported in which the pesticide ingredient is dissolved in a large amount of organic solvent to formulate a formulation, but these organic solvents have problems such as odor, flammability, and phytotoxicity to plants. Moreover, in order to obtain a wettable powder containing a large amount of organic solvent or a granular wettable powder with good physical properties, it is necessary to add a large amount of surfactant, which increases the cost. Many issues remained.

Means for Solving the Problems> As a result of various studies to solve the above-mentioned problems, the present inventors discovered a solid pesticide formulation with good long-term storage stability and completed the present invention. That is, the present invention has a melting point of 0 to 70
°C, and one or more water-soluble compounds selected from polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxybutylene glycol, and polyoxyethylene polyoxypropylene polyoxybutylene glycol, which are solid at room temperature. The molten mixture obtained by heating and melting the polymer with or without the addition of a surfactant and/or solvent is cooled and solidified, and then a mineral carrier is added thereto,
By mixing, with or without the addition of further formulation auxiliaries, or by adding a mineral carrier to the molten mixture and cooling and solidifying, with or without the addition of further formulation auxiliaries, as required. The present invention provides solid pesticide formulations obtained by pulverization, granulation, etc.

Incidentally, the term "pesticide active ingredient" as used herein does not necessarily mean a single compound, but also includes a mixture of two or more kinds of compounds. In that case, the melting point of the mixture is 0 to 7.
The target temperature is 0℃.

Examples of the polyethylene glycol used in the present invention include those having an average molecular weight of too much or more, and particularly those having an average molecular weight of 4000 to 200 from the viewpoint of water solubility.
00 is preferred.

As polyoxyethylene polyoxypropylene glycol, the weight of ethylene oxide in the molecule is usually 80%.
Above, and the average molecular weight of the propylene oxide moiety is too much or more.

As polyoxyethylene polyoxybutylene glycol and polyoxyethylene polyoxypropylene polyoxybutylene glycol, the weight of ethylene oxide in the molecule is usually 80% or more, and the average molecular weight of the butylene oxide part or propylene oxide part is 10.
00 or more is used.

Here, the term "solid state at room temperature" specifically means that the melting point is about 30°C or higher.

Specific examples of water-soluble polymers such as polyethylene glycol have an average molecular weight of 1000.4000.6000.10.
000.20000 polyethylene glycol (hereinafter referred to as
PEG-1000, PEG-4000, respectively
PEG-6000, PEG-10000, PEG
It is written as G-20000. ), Newport PE-6
8 (manufactured by Sanyo Chemical Co., Ltd., the weight of ethylene oxide in the molecule is 80%, the average molecular weight of the propylene oxide part is 1
750 polyoxyethylene polyoxypropylene glycol), Newpol ■PE-78 (same as above, polyoxyethylene polyoxypropylene glycol with an ethylene oxide weight of 80% in the molecule and an average molecular weight of the propylene oxide portion of 2050), Newpol ■PE-78 -8
8 (same as above, the weight of ethylene oxide in the molecule is 80%, and the average molecular weight of the propylene oxide part is 2250 polyoxyethylene polyoxyprobi I / glycol), Niepole PE-108 (same as above, the weight of ethylene oxide in the molecule is 80%) %, polyoxyethylene polyoxypropylene glycol whose propylene oxide moiety has an average molecular weight of 3250), and these may be used alone or in an appropriate mixture. The amount used is usually 30 to 900% by weight, preferably 70 to 3% by weight based on the agricultural chemical ingredient.
00% by weight.

In the present invention, a surfactant may be added when melting the agricultural chemical ingredient and the water-soluble polymer, and examples of the surfactant used include glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, and fatty acid salt. , alkyl sulfate ester, alkylbenzene sulfonate, alkyl amine salt, quaternary ammonium salt, alkylaryl ether and its polyoxyethylenic product, higher alcohol ethylene oxide adduct, Newpol PE
-64 (manufactured by Sanyo Kasei Co., Ltd., polyoxyethylene polyoxypropylene glycol with an ethylene oxide weight of 40% in the molecule and an average molecular weight of the propylene oxide portion of 1750), which is a liquid or paste polyoxyethylene polyoxypropylene at room temperature. Examples include glycols, and these may be used alone or in arbitrary mixtures. These surfactants preferably become liquid when heated and melted, and the amount added is 0.1 to 20% by weight, preferably 1 to 10% by weight in the preparation.

If the viscosity is high during heating and melting, a small amount of solvent may be added if necessary. As the solvent, a nonvolatile solvent or a low volatility solvent is usually used. Solvents used for the purpose of adjusting viscosity include those with an average molecular weight of 200 to
Polyethylene glycol that is liquid at room temperature of 600℃,
Polypropylene glycol, glycol ethers, etc. are preferred, but vegetable oils, mineral oils, liquid paraffin, aromatic hydrocarbons, etc. are also used, and the amount added is usually 200% by weight or less, preferably 50% by weight, based on the agricultural chemical raw material. %
It is as follows.

Specific examples of agricultural chemical ingredients used in the present invention are shown below, but the present invention is not limited to these examples.

(1) α-cyano-3-phenoxybenzyl 2-(4
-chlorophenyl)-3-methylbutylade (S)-α-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-
Methyl butylade α-cyano-3-phenoxybenzyl 2.2,3.3-tetramethylcyclopropanecarboxylate 3-phenoxybenzyl 3-(2゜2-dichlorovinyl)-2,2-dimethylcyclopropane lupoxylate 3 -Phenoxybenzyl chrysanthemate α-cyano-3-phenoxybenzyl 2-dimethylcyclopropanecarboxylate (7) α-cyano-3-(4-fluorophenoxy)benzyl 3-(2,2-dichlorovinyl)-2, 2
-dimethylcyclopropane lupooxylate α-cyano-3-(3-bromophenoxy)benzyl 3-(2,2-dichlorovinyl)-2
,2-dimethylcyclopropaneylpoxylate α-cyano-3-(4-chlorophenoxy)benzyl 3-(2,2-dichlorovinyl)-2
,2-dimethylcyclopropanecarboxylade α-cyano-3-(4-bromophenoxy)benzyl 3-(2,2-dibromovinyl)-2
,2-dimethylcyclopropanecarpoxylate α-cyano-3-phenoxybenzyl chrysanthemate (lO) 3-(2,2-dichlorovinyl)-2°(12)
α-cyano-3-(4-bromophenoxy)benzyl
2-(4-chlorophenyl)-3-methylbutylade (13) α-cyano-3-(3-bromophenoxy)benzyl 2-(4-chlorophenyl)-3-methylbutylade (14) α-cyano-3 -(4-chlorophenoxy)benzyl 2-(4-chlorophenyl)-3-methylbutyrad (15) α-cyano-3-(4-fluorophenoxy)benzyl 2-(4-chlorophenyl)-3-methylbutylade (16) α-cyano-3-phenoxybenzyl 2-
(4-bromophenyl)-3-methylbutyralide (17) α-cyano-3-phenoxybenzyl 2-
(4-tert-butylphenyl)-3-methylbutylade (18) α-cyano-3-phenoxybenzyl 2-
(3,4-methylenedioxyphenyl)-3-methylbutylade (19) α-cyano-(4-fluoro-3-phenoxy)benzyl 3-(2,2-dichlorovinyl)-
2,2-dimethylcyclopropane lupoxylate (20) α-cyano-3-phenoxybenzyl 2-
Chloro-4-(trifluoromethyl)anilino-3-methylbutyralide (21) α-cyano-3-phenoxybenzyl 2-
(4-Difluoromethoxyphenyl)-3-methylbutylade (22) Cyano-(5-phenoxy-2-pyridyl)methyl 3-(2,2-dichlorovinyl)-2,2-
Dimethylcyclopropane lupoxylate (23) α-cyano-3-phenoxybenzyl 2.
2-Dimethyl-3-(1,2,2゜2-tetrabromoethyl)cyclopropane lupoxylate (24) α-cyano-3-phenoxybenzyl2.
2-dimethyl-3-(1,2-dichloro-2,2-dibromoethyl)cyclopropane lupooxylate (25) α-cyano-3-phenoxybenzyl 1
-(4-ethoxyphenyl)-2,2-dichlorocyclopropane lupoxylate (26) α-cyano-3-phenoxybenzyl 2
．． 2-dimethyl-3-(2-chloro-3-trifluoromethylvinyl)cyclopropane lupoxylate (27) 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (28) 3-phenoxybenzyl 2-(4-ethoxyphenyl)-3,3,3-)lifluoropropyl ether (29) O,O-dimethyl-3-(N-methylcarbamoylmethyl)phosphorodithioate (30) O-5ec-butyl Phenyl N-methylcarbamate (31) N-(chloroacetyl)-N-(2゜6-
(dinitylphenyl)glycine ethyl ester These agricultural chemical ingredients are usually contained in the formulation in an amount of 0.1 to 60% by weight.
Preferably it is contained in an amount of 1 to 40% by weight.

The agricultural chemical solid formulation of the present invention is produced, for example, as follows.

Water-soluble polymers such as polyethylene glycol and polyoxyethylene polyoxypropylene glycol, which are solid at room temperature, are heated in a container to 50°C or higher, usually 80 to 95°C, and are heated to an interface with the agricultural chemical substance, if necessary, while stirring. Add activator and/or solvent and mix uniformly. After cooling and solidifying the molten mixture obtained in this way, a mineral carrier is added, and if necessary, formulation auxiliaries such as stabilizers, fixing agents, and dispersants are added, and wettable powders, powders, and granules are prepared according to known methods. It can be formulated into solid pesticide preparations such as granular wettable powders. Moreover, 1. A mineral carrier and, if necessary, a formulation auxiliary agent may be added to the molten mixture, followed by cooling and solidification to formulate a solid agricultural chemical formulation.

Mineral carriers used in the present invention include, for example, clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasamiclay acid clay, etc.), talcs, and other inorganic minerals (sericite, quartz, sulfur, activated carbon, carbonate, etc.). Calcium, hydrated silica, etc.), etc.), and the amount used varies depending on the dosage form, but is generally 5 to 99% by weight, preferably 20 to 90% by weight.
%.

Examples of formulation aids such as fixing agents and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, sugars, and synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, etc.). methylcellulose, polyacrylic acids, etc.), and PAP (isopropyl acid phosphate) and the like can be mentioned as formulation aids as stabilizers.

<Examples> The present invention will be explained in more detail below using production examples and test examples, but the present invention is not limited to these examples.

In addition, in the following manufacturing examples, parts represent parts by weight.

Production Example 1 Compound (10 parts of PEG-4000 was added to 3NO part, heated and melted at 80°C and mixed well. 5 parts of synthetic hydrous silicon oxide and toxanone [F] PSW-46 were added to the molten mixture.
(Surfactant manufactured by Sanyo Kasei Co., Ltd.) 3 parts and diatomaceous earth 7
2 parts were added, mixed thoroughly with a juice mixer, and then cooled to room temperature. The mixture was then ground and mixed using a centrifugal grinder to obtain the wettable powder of the present invention.

Production Example 2 A hydrating agent of the present invention was obtained in exactly the same manner as in Production Example 1 except that PEG-6000 was used instead of PEG-4000.

Production Example 3 The hydrating agent obtained in Production Example 1 or 2 was placed in a dish-type rolling granulator and granulated without spraying water. The obtained granules were dried at 40°C and sized to 1000 to 297μ,
A granular wettable powder of the present invention was obtained.

Production Example 4 10 parts of compound (2), (4), (5) or (6),
Add 10 copies of Nieuport PE-68 (mentioned above), 80
The mixture was melted by heating to 0C and mixed well. To the molten mixture were added 5 parts of synthetic hydrated silicon oxide, 3 parts of toxanone PSW-46 (the above-mentioned surfactant), and 72 parts of diatomaceous earth, mixed thoroughly with a juice mixer (-then cooled to room temperature), and then mixed with a centrifugal pulverizer. The mixture was crushed and mixed to obtain the wettable powder of the present invention.

Production Example 5 To 0.5 parts of compound (4), 1 part of PEG-20000 or Newport PE-78 (described above) was added, and 8 parts of
The mixture was melted by heating to 0°C and mixed well. 1 part of synthetic hydrous silicon oxide, 0.3 part of P A P and 97.2 parts of kaolin clay were added to the molten mixture, mixed well with a juice mixer, and then cooled to room temperature. The mixture was then ground and mixed using a centrifugal grinder to obtain the powder of the present invention.

Production Example 6 0.8 part of PEG-6000 or Newport PE-108 (described above) was added to 0.5 part of compound (2), and the mixture was heated and melted at 80°C and mixed well. To the molten mixture were added 1 part of synthetic hydrous silicon oxide, 4 parts of Tsurupol ■5060 (surfactant manufactured by Toho Chemical Co., Ltd.), 30 parts of bentonite, and 64.7 parts of talc, and the mixture was thoroughly mixed with a juice mixer and then cooled to room temperature. Add water to this (
After kneading, the mixture was extruded and granulated using a 0.9 mmφ screen using a vertical granulation machine. Next, this was dried at 40° C. and sized to a size of 1680 to 297 μm to obtain the granules of the present invention.

Production Example 7 30 parts of PEG-200000 was added to 10 parts of compound (3) and heated and melted at 80°C (mixed). The molten mixture was spread on a glass plate, cooled and solidified, and then crushed. Synthesized hydrous silicon oxide 10 parts, toxanone @PSW
3 parts of -46 (the above-mentioned surfactant) and ±47 parts of diatoms were added, mixed well, and then ground and mixed using a centrifugal grinder to obtain a wettable powder of the present invention.

Production Example 8 To 3110 parts of the compound, 3 parts of polyethylene glycol with an average molecular weight of 200 and 20 parts of PEG-400 were added, and the mixture was heated and melted at 80°C (mixed). 10 parts of synthetic hydrous silicon oxide and toxanone were added to the molten mixture. ■PSW-4
6 (the above-mentioned surfactant) and 54 parts of diatomaceous earth were added and mixed well, and then ground and mixed using a centrifugal grinder to obtain a wettable powder of the present invention.

Comparative Example 1 3110 parts of the compound was heated and melted at 70°C, 5 parts of synthetic hydrous silicon oxide, 3 parts of toxanone PSW-46 (the above-mentioned surfactant) and 182 parts of diatom were added, and mixed with a juice mixer. The mixture was then cooled to room temperature, and then ground and mixed using a centrifugal grinder to obtain a wettable powder.

Comparative Example 2 10 parts of compound (3) was heated and melted at 70°C, 5 parts of synthetic hydrous silicon oxide, 3 parts of toxanone PSW-46 (the above-mentioned surfactant) and 72 parts of diatomaceous earth were added and mixed well with a juice mixer. After that, it was cooled to room temperature. 10 parts of powdered PEG6000 was added to this, mixed in a juice mixer, and then ground and mixed in a centrifugal grinder to obtain a wettable powder.

Comparative Example 3 5 parts of synthetic hydrous silicon oxide was added to 10 parts of solid pulverized product of compound (3).
part, toxanone ■PSW-46 (the above-mentioned surfactant) 3
172 parts of diatoms and powdered PEG-600
010 parts were added and mixed well with a juice mixer, and then ground and mixed with a centrifugal grinder to obtain a wettable powder.

Test Example 1 100 g of each of the hydrating agents obtained in Production Example 1 and Comparative Example 1.2.3 was sealed in an aluminum bag, and 50 g of each was stored at 0°C for 30 days and at 40°C for 30 days. Take, 45
A wet sieving test was carried out using a μ sieve, and the residue on the sieve was transferred to an evaporating dish, dried and weighed, and the proportion passing through the sieve was expressed as fineness in weight %. The results are shown in Table 1 together with the results immediately after manufacture.

After sampling 25 ml and evaporating the water, it was analyzed by gas chromatography to determine the suspension ratio.

The results are shown in Table 2.

Test Example 2 The suspension ratio of each of the hydrating agents in Test Example 1 was measured by the method shown below.

250ml of 3° hard water was placed in a constant temperature water tank at 20°C.
A 50m1 cylinder with a common stopper was installed, and each hydrating agent 5
00 mg was placed in the cylinder and suspended, and after 15 minutes, each particle was released from the center of the cylinder. <Effects of the Invention> The solid agricultural chemical formulation of the present invention has excellent storage stability, and its physical properties remain unchanged even when stored for a long period of time. This is an excellent product with extremely little deterioration.

Claims (3)

[Claims] (1) Pesticide active ingredients with a melting point of 0 to 70°C and polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxybutylene glycol, and polyoxyethylene polyoxypropylene polyoxybutylene that are solid at room temperature. A mineral carrier is added to a molten mixture obtained by heating and melting one or more water-soluble polymers selected from glycols with or without adding a surfactant and/or a solvent, and solidifying the molten mixture by cooling. and mixing, with or without the addition of further formulation auxiliaries, or adding a mineral carrier to the molten mixture and cooling and solidifying with or without the addition of further formulation auxiliaries. A method for producing a solid pesticide formulation characterized by the following. (2) A solid agricultural chemical formulation manufactured using the manufacturing method according to claim (1). (3) One or more water-soluble polymers selected from polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxybutylene glycol, and polyoxyethylene polyoxypropylene polyoxybutylene glycol have a 70% The method for producing a solid agricultural chemical formulation according to claim (1), wherein the amount is 300% by weight.